Cycloalkanecarboxamide herbicides



United States Patent 3,277 171 CYCLOALKANECARBdXAMIDE HERBICIDES Thomas R. Hopkins, Overland Park, Kans., assignor, by mesue assignments, to Gulf O'fl Corporation, Pittsburgh,

Pa., a corporation of Pennsylvania No Drawing. Filed Mar. 28, 1963, Ser. No. 268,581 Claims. (Cl. 260-557) This invention relates to novel chemical compounds, herbicidal compositions containing said novel chemical compounds as an active ingredient and to methods for controlling plant growth with such herbicidal compositions.

There are provided by this invention novel chemical compounds conforming to the formula:

wherein n has a value 01; R is selected from the group consisting of alkyl groups, aryl groups, and halogen atoms; and R and R are independently selected from the group consisting of hydrogen, alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, heterocyclic groups, and, when taken together with the nitrogen atom to which R and R are attached, a heterocyclic radical. For convenience in description, the above compounds subsequently will :be referred to simply as cyclo: alkane carboxamides. As will be seen, the compounds of this invention are either unsubstituted amides or amides having one or more organic substituents on the nitrogen atom.

The cycloalkane carboxamides above described can be formulated with inert carriers, emulsifiers and the like to provide herbicidal compositions that can be used effectively to control plant growth. The resulting herbicidal compositions can be used as either pre-emergent or postemergent herbicides.

The following examples are set forth to illustrate more clearly the principle and practice of this invention to those skilled in the art.

EXAMPLES I-VI Four amides of l-methylcyclopropane carboxylic acid are prepared by reacting methyl l-methylcyclopropane-lcar-boxylate with, respectively, 3-chloroaniline, 3-chloro- 4-methylaniline, 2-methyl-5-chloroaniline, and 3,4-dichloroaniline.

In each synthesis 0.] gram :mol of methyl l-methyl' cyclopropane-l-carboxylate, 0.1 gram mol of the amine, 0.11 gram mol of sodium methoxide and 200 ml. of henzene are stirred and heated to gentle reflux. Reflux is continued for about 12 hours while the benzene-methanol azeotrope is removed as formed. The reaction mixture is cooled to room temperature and there is then added thereto 50 ml. of water and 15 ml. of concentrated hydrochloric acid dissolved in 40 ml. of water. After thorough mixing, the organic phase is recovered by decantation and is successively extracted with dilute hydrochloric acid. and water. The organic phase is dried and decolorized with carbon. After removal of the benzene under reduced pressure, the resulting amides are recrystallized from ligroin. The identification of the amides prepared (Examples I, II, III, and VI) and their melting points are set forth in Table I.

Three amides of l-methylcyclopropane carboxylic acid are preferably prepared by an alternative procedure, in which l-methylcyclopropane carbonyl chloride is reacted with 2,6-dichloroaniline, 2,6dimethylaniline, and 2,5-dimethylaniline, respectively. The acid chloride is prepared conveniently by reacting a solution of 7.8 grams (0.078 mol) of l-methylcyclopropane carboxylic acid with ml.

3,277,171 Patented Oct. 4, 19.66

of thionyl chloride by standing for about 16 hours, followed by removal of excess thionyl chloride by distillation under reduced pressure. The residue, which consists essentially of l-methylcyclopropane carbonyl chloride (boiling point 132-134 C. at 760 mm. Hg), is then reacted with the substituted aniline compound without further purification by the procedure set forth in section D under Example VII below, or by other procedures which are known to workers skilled in the art. The identification of the amides prepared (Examples IV, V, and Va) and their melting points are set forth in Table I.

Table l Amide N-(8-chlorophenyl) -1-methy1cyclo-pr0pane-1- carboxamide. N-(3-chloro 4-methylphenyl)el-methylcyclopropane-l-carboxamide'. N-(2-methyl-5-chlorophenyl)-1-methyleyclopropane-l-carboxamid N-(2,6-dichlor0phenyl)-1-methylcyc1opropane l-earboxamide. N-(2,6-dirnethylpheuyl)-1-methylcyclopropane-l-carboxamide. N-(2,5-dimethylphenyl)-1-methylcyclopropaue-l-carboxamide. N -(3,4-dichlorophenyl)-1-methyleyclopropane-l-carboxamide.

EXAMPLE VII Part A.-A solution of 20.1 grams (0.3 mol) of cyclopropane-l-carbonitrile, 45.2 grams (0.33 mol) of freshly distilled butyl bromide and 500 ml. of benzene is heated to 76 C. A slurry of sodium amide in benzene (freshly prepared from 6.9 grams (0.3 gram atom) of sodium in 150 1111. of benzene) is added slowly to maintain reflux and external heating is discontinued. After the addition of the sodium amide is completed, external heat is again applied and the mixture is refluxed for 24 hours. Thereafter, an additional 12 grams of butyl bromide is added to the reaction mixture and re flux is continued for an additional 24 hours. The reaction mixture is then cooled, extracted successively with water, dilute phosphoric acid and another portion of water, and finally dried. The benzene is removed by distillation at reduced pressure and the product is vacuum distilled to give 9.5 grams of liquid which boils at 68-70 C. at 7 mm. Hg and has a refractive index of 1.4326 at 19 C. The product is 1 buty lcyclopropane-l-carbonitrile.

Part B.A mixture of 13 grams (0.106 mol) of 1- butylcyolopropane-l carbonitrile and 34 grams (0.26 mol) of sulfuric acid is stirred and heated at -135" C. for 1 hour. The solution is then cooled and maintained below 60 C. while 14.6 grams (0.212 mol) of sodium nitrite is added in small portions to facilitate hydrolysis of the nitrile group. After the addition of the sodium nitrite has been completed, the reaction mixture is stirred at room temperature for 1 hour and then poured onto ice. The organic phase is taken up in a small quantity of ether and dried. The material, after removing the ether, is distilled to give l butylcycloprop-ane-l-carboxyl-ic acid which has a boiling point of 89-94 C. at 1 mm. Hg and a refractive index of 1.4496 at 19 C.

Part C.A solution of 11 grams (0.078 mol) of 1- butylcyclopropane-lcarboxylic acid and 20 ml. of thionyl chloride is permitted to stand for 16 hours at 25 C. and then refluxed for 2 hours. The excess thionyl chloride is removed under reduced pressure and the residue is vacuum distilled to give 9.7 grams of l-butylcycloprop-ane-l-carbonyl chloride which has a boiling point of 6769 C. at 10 mm. Hg.

Part D.-The acid chloride prepared in part C is added slowly to a stirred solution containing 9.8 grams (0.064

mol) of 3,4-dichloroaniline, 5.06 grams (0.064 mol) of pyridine and 100 m1. of benzene. Thereafter, 100 ml. of ethyl acetate is added and the reaction mixture is refluxed for 2 hours. The reaction mixture is cooled, and successively extracted with water, dilute hydrochloric acid, water, dilute sodium bicarbonate solution and water. The organic solution is then dried and decolorized with carbon. The solvents are removed under reduced pressure and the residue is then recrystallized from heptane to give 15.1 grams of product which melts at 118.5120 C. The product is N-(3,4d-ichlorophenyl)-1-buty1cyclopropane-carboxamide.

EXAMPLES VIII-)QII A series of amides are prepared by reacting l-chlorocyclopropane-l-carbonyl chloride (prepared by the method of Bruylanta [Acad. Royale De .Belgique Bulletin (1921), 705]) with respectively, p-phenylazoaniline, pacetylaniline, 3,4-dichloroaniline, 3-chloroaniline and 3- chloro-4-methylaniline by the procedure described in Example VII, part D. The amides prepared and their meltnig points are set forth in Table II.

per acre rate of application.

EXAMPLE XVII A water suspension of the chemical is prepared by combining 0.4 gram of the chemical to be tested with 4 of a solvent mixture (3 parts Emulphor EL-719 combined with one part xylene and one part kerosene) and then adding suflicient warm water to make 40 m1. ofrnixture. Emulphor EL-719 is described as a polyoxyethylated vegetable oil.

Oats, wheat, peas, radish, flax, millet, alfalfa, tomatoes, and sugar beets are planted in 4" pots in the greenhouse. Ten to eighteen days after the emergence of the plants, they are sprayed with the above prepared water emulsions Table II at a rate of 5 pounds of the active chemical per acre and Example Amide MB of a sprayvolume of 60 gallons per acre. Seven days after, Amide C. apphcation, the plants are observed and the results of the treatment are as shown in Table IH. VIII N-p-(bphenylgzo)phenyl-l-chloroeyclopropane- 196-198 Th l t ar rat d a follgws;

C8! OXaIIll 8. IX N-(p-acetylpher1yl)-l-ehloroeyclopropane- 183-185 X Ncalgboxal l'dhel. I b 6M3 C=Ohloros1s 0=No eifect -p eny- -c orocyc opropanecar oxami e XI N-(3,-chloroiphenyl)-i-chlorocyclopropane- 95-96 N=Necrosls 5-3 51 eflectfi t car oxami e. I at e ec XII N-(3-ehlorophenyl)-1-chlorocyciopropane- 73-74 G Growth mhlbmon Ncarbgrlramide. th 1 h I) 1 m 89 90 K=Non-emergence 3=Severe effect XIII -(3-c oro-4-rne y p euy -e orok eyclopropanecarboxamide. F Format1ve eflect 4 MaXlIlTllm efiect i I or dead plants Table III Compound Oats Wheat Soy- Radish Flax Millet Alfalfa Tomato Sugar beans Beets N-(3 4-diehloro hen l-l-meth leyclopropanecarboia n e p 1 y) 1 1 N4 N4 1 N4 N4 N4 N4 N4 N4 N-3-c oro hen -1-rneth e 0 r0 anecarlEmmmide y) y y p p N1G1 N4 N4 N4 N4 N4 N4 N4 N-phenyl-bchloroeyclopropanecarb oxamide 0 G1 0 0 N2 N 1 C 1 0 G1 N-(3,4-dichlorophenyl)-l-methylcyclopropaneearbnxamidn N3 N2 1 C2 N4 N3 N4 N4 0 N 4 N-phenyl-l-phenylcyclopropanecarboxarnide 5---- 0 0 0 0 0 0 0 0 0 N-(3-chlorophenyl-1-chlorocyclopropauecarboxamide G 1 0 N1 N2 N3 0 N 2 N1 N 1 N-(3-ehl0ro4-methylphenyl)-lchlorocyclopropanecarbnrarnide O 0 N1 N2 N1 M3 N2 N1 N3 N- 3-chloro-4-n1eth i hen l-l-meth lo 010 ro anec irboxamidmujfuniz inin N2 G2 N1 N3 N3 N4 N3 N4 N-(3,4-dichlorophenyl)-1-butylcyclopropanecarboxamidp 0 0 N1 0 N1 0 N 0 N- 2,6-dichloro hen l-leth lo 010 ro aueear- ];mmmidP p y) m y y p O O 0 O O 0 U 0 0 N-(2 fi-dimeth l hen l-l-meth lc'clo r0 anecar- -hn;mmido yp y y p p 0 o o o 0 0 0 0 0 N-(5-chl0ro-2-meth l hen I-l-meth 10 010 ro aneearboxamideuni njl lin C1 C1 C2 C3N1 Cl G2N2 N302 N2 N4 N-(3,4-dichlorophenyl)-1-bromoeyclobutanecarboxamiria 0 0 l 0 N2 N2 N4 N2 0 N2 N-pheuyl-l-br'omocyclobutanecarboxamide 0 0 1 0 N2 N1 N4 N2 0 N1 I 1 Peas used in these trials.

EXAMPLE xiv EXAMPLE XV N-phenyl-l-bromocyclobutanecarboxamide is prepared by reacting 1-bromocyclobutane-l-carbonyl chloride with aniline following the procedure described in Exampl XIV. The compound melts at 8990 C.

' The following example illustrates the activity of many of the compounds of this invention as pre-emergent herbicides at a 10 pounds per acre rate of application.

EXAMPLE XVHI Disposable paper half-flats are seeded and sprayed with the acetone solutions at a rate tov give 5 pounds of the active compound per acre. One flat, which has been seeded with alfalfa, brome, flax, oats, radishes, and sugar beets, is held at 75 F. day temperature; another flat which has been seeded with corn, coxcomb, cotton, crabgrass,

millet, and soybeans is held at 85 F. Twenty-one days after seeding and treatment the flats are examined, plant emergences and chemical efiects on the seedlings are rated and are as shown in Table IV. The rating system em- 6' nitrogen atom to which R and R are attached, a heterocyclic group. In a preferred group of the compounds conforming to the above formula, R is a hydrogen atom and R is a monocyclic aryl group such as the phenyl ployed is the same as in Example XVH. 5 group and the nuclearly substituted phenyl groups. In

Table IV Compound Alfalfa Brome Flax Oats Radish Sugar Corn Cox- Cotton Crab- Millet Soy- Beets comb grass beans in h 1-1- th 1- c igfi gfigafimifi wI"--- N4 N4 N4 N4 N4 N4 N3 N4 N4 N4 N4 N4 N-(3-chlorophenyD-l-methylcyclopropanecarboxamide N4 N4 N3G4 N4 N3 N4 G2 N4 G2 N2 N4 G3K3 N-phenyl-Lchlorooyclopropaneearboxamide 0 0 0 0 0 0 0 0 0 0 0 N(3,4-dichlorophenyl)-l-methyl- N4 N3 N2 N2 N4 N4 0 N4 0 N4 N4 C2K2G3 cyteloprloparlilecarlmxalmide t rfifiiamfieffiiii239%-- 0 o o o 0 0 0 0 0 0 0 0 1 -1- 1 i ogtiiie a i ii rind ???3 .i- N4 K4 G2 G2 0 0 K2G2 N4 G2 N2G2 N3G2 K4 N-3-hl -4 th 1 h 1-1- chlcfrogyglog pa e afl xamide N3 0 0 0 0 0 G1 N4 0 N2G2 N3G2 K4 N-(3 chloro-4-methylphenyl)-1- metal 13 1egfloprfipaufcargoiainideh N3 N1 N2K2 0 0 N2 0 N4 0 0 0 0 3 cg olop gp r r agh xl nlud gi i 0 0 0 0 0 0 0 0 0 0 O 0 ity cigfi ililiafi inl -1;"- G2 N4 N1 K3N1 o2 N1 N1 0 0 N2 N3 N2 1 1-1- th cgeiogifiiiclfg hifii -Y N4 N1 N1 N1 N1 N1 N1 N2 0 N2 N3 N1 1 h xitifli igcigf niic$riamida N4 N4 N4 N4 N4 N4 04 N4 0 C4 C4 C4 1 egiififiiafififirfiinmi??? N4 0 N2 0 0 0 0 N4 0 0 N4 G2 o 0 0 0 0 K2 0 o 0 0 0 0 EXAMPLE XIX the special case when R is a monocyclic aryl group, R

can be a hydroxy group. -g y F P Examples of nitrogen substituents represented by R carboxamlde teSPed as Pre'emergimt hen-blade by the and R in the above formula are alkyl groups, and espe i q described m Example Xvm except that cially the lower alkyl groups having from about 1 to about Phcatlon rates are 3 and 1 Pounds Per acre 6 8 carbon atoms, either straight or branched chain; cyclo sults are as Shown Table alkyl groups, especially the cyclic lower alkyl groups T H V having about 3 to 8 carbon atoms; alkenyl and alkynyl a e 40 groups, and especially the lower alkenyl and alkynyl groups having about 2 to about 8 carbon atoms; aralkyl il g Alfalfa Bmme Flax Oats Radlsh gig groups and especially the monocyclic aralkyl groups such as benzyl and nuclearly substituted benzyl groups; aralkyl N4 N4 N4 Cam N4 N4 groups, and especially the monocyclic aryl groups such as N4 N4 03 C2 84 g: the lphenyl group and nu-clearly substituted phenyl, groups N4 03 C1 C1 4 having nuclear substituents such as halo, and especially chloro, iodo, fluoro and bromo, alkoxy and especially Application Corn 0014- Cotton Crab- Millet Soylower alkoxy groups containing 1-8 carbon atoms, cyano, Rate comb grass beans nitro, alkyl and especially lower alkyl groups containing N4 C3 1-8 carbon atoms, acyloxy and hydroxy; and heterocyclic 8g fig 3 3% N4 C2 groups, especially monocyclic groups having at least one 02 N3 0 C4 C4 C2 nitrogen, oxygen or sulphur atom (or two or more hetero atoms) in addition to carbon in the ring. R and R also may be linked together with the amide nitrogen atom These data Show that N'(g.m?thyl's'chlorophenyl) 1 to constitute a heterocyclic radical, such as the monocyclic methylcycl-o-propanecarboxamlde is an excellent pre-emerradicals 0 11,, mtrogen, oxygen, or sulphur 1n addition gent herblclde for some crops, such as alfalfa, brome, coxb d ulafl crab ass at a plicafion rates as to carbon 1n the ring, for example the amldes formed from T3 p z g g z gr p piperidine, piperazine, morpholine, and the like.

The cycloal kane carboxamides provided by this inven- RQpresnt,at1ve examples of radlcals Tepresented by tion conform to the formula: R and R 1n the above formula are hydrogen, methyl, ethyl, 2-chloroethyl, 2-hydroxyethyl, propyl, isobutyl, H20 R1 0 pentyl, isooctyl, allyl, butenyl, pentenyl, butynyl, 4-chloro- (1120) g Z-butynyl, propynyl, phenyl, naphthyl, 3-chlorophenyl, 1 l 3-iodophenyl, -3-fiuorophenyl, 4-bromophenyl, 3.4-dichlo- H20 2 rophenyl, 2,4,5-trichlorophenyl, 3-methylphenyl, 3,4-diwherein n has a value of 0-1; R is selected from the bromophenyl, 2,5-difluorophenyl, 4-cyanophenyl, 3,5-digroup consisting of alkyl groups which preferably contain nltrophenyl, 4-hydroxyphenyl, 3-chloro-4-methylphenyl, 1-8 carbon atoms, aryl groups, preferably monocyclic 4-acet0xyphenyl, 3-methoxyphenyl, 3-trifiuoromethylaryl groups such as phenyl, t-olyl, xylyl, etc., and halogen phenyl, cyclopropyl, cyclohexyl, cyclobutyl, 4-cycloatoms such as fluorine, chlorine, bromine, and iodine; and propylcarbonyloxyphenyl, benzyl, 3,4-d1chlorobenzyl, 2- R and R are independently selected from the group conthiazolyl, 2-pyr1dyl, and triazolyl. Compounds having a sisting of hydrogen, alkyl groups, cycloal-kyl groups, al-kecyclic radical in which the amide nitrogen atom is part of nyl groups, alknyl groups, aryl groups, aralkyl groups, the ring are formed from compounds such as piperidine, heterocyclic groups, and, when taken together with the morpholine and pyrrolidine.

A preferred subgroup of compounds which constitute a preferred embodiment of the invention conform to the formula set forth below:

(kg R:

wherein R R and R have the same meaning as previously set forth.

Another more limited group of'compounds which constitute an especially preferred embodiment of the invention conform to the formula set forth below:

R1 meats- K. $5. 1'1 I wherein R has the meaning previously set forth; and X and X; are independently selected from the group consisting of hydrogen, fluorine, chlorine and a methyl group with the further provision that at least one of said X substituents is a chlorine or fluorine atom.

The cycloalkane carboxamides of this invention can be readily prepared by the reaction of cycloalkane carboxylic acid halides such as the acid chlorides, with an appropriate amine. Preferably, the reaction is run in the presence of an inert organic solvent such as cyclohexane, toluene, dioxane, benzene, n-hexane or n-pentane. Since hydrogen halide is a byproduct of the reaction, it is desirable to use a molar excess of the amine or, preferably, a tertiary amine such as triethylamine or pyridine, to react with the hydrogen halide that is evolved, thereby improving the yields and purity of the desired product. This reaction runs smoothly at room temperature or slightly below room temperature and normally is completed in about 0.5 to 2 hours. A preferred reaction temperature is about to 25 C., which temperatre is sufiiciently low to maintain good control of the reaction. To make full use of the reactants, it is preferred to add the cycloalkane carboxylic acid halide to a solution of the amine (and tertiary amine hydrogen halide acceptors if used) in an organic solvent, thus maintaining an excess of amine during the reaction period. When an organic solvent for the cycloalkane carboxamide is used, the byproduct pyridine hydrohalide can be removed by filtration and the desired cycloalkane carboxamide can be isolated from the solvent by known procedures. The crude amine can be recrystallized from solvents such as water-alcohol mixtures, n-hexane or ethyl acetate. When the reaction product is a liquid, it can be purified by distillation under reduced pressures.

In an alternative and preferred procedure the cycloakane carboxa-mides can be prepared by reacting an ester of an appropriate cycloalkane carboxylic acid with the appropriate amine in the presence of an equimolar quantity of an alkali metal alcoholate. This method is more fully escribed and claimed in the copending application of Richard De Feo, Serial No. 265,372, filed March 15, 1963, and assigned to the assignee of the present application. The description of this copending application is incorporated herein by reference.

The cycloalkane carboxamides in which X of the first formula appearing above'is sulfur can be prepared from their oxygen analogues by sulfurization with phosphorus pentasulfide at an elevated temperature, e.g., about 1l,0 C.

The cycloalkane carboxamides of the invention can be used as herbicides at application rates of from about 20 pounds to as little as about 0.1 pound per acre. When the compounds are used as a pre-emergent herbicide, an application rate of about 0.5 to about 20 pounds per acre is normally used, with about'2 to about 10 pounds per acre being preferred. When they are used as a postemergent herbicide, an application rate of about 0.01 to 20 pounds of one or more active compound per acre is used, with an application rate of about 0.1 to 3 pounds per acre being preferred. When using a water emulsion of the herbicide, a spray volume of about 1 to about gallons of aqueous emulsion, and preferably about 5 to 40 gallons, per acre is used.

The cycloalkane carboxamides of the present invention show good activity against a number of plant species. They also show better selectivity against a number of closely related species than is usually observed with compounds having such a high degree of activity. The selectivity of kill can be enhanced by proper formulation and control of application rates. The cycloalkane carboxamides have a high degree of resistance to most of the common soil microorganisms and, when used as preemergent herbicides, provide a high degree of control over an extended period of time.

Certain species of the .l-substituted cyclopropanecarboxamides, particularly N-(2-methyl-5-chlorophenyl)-1- methylcyclopropanecarboxamide, appear to have substantial utility as pre-emergent herbicides in controlling crabgrass in bluegrass lawns.

The excellent herbicidal activity of the cycloalkanecarboxamides of this invention requires the application of only small amount-s of the active ingredient distributed uniformly over a wide area. Of course, this is diflicult to do employing the pure material. However, by increasing the bulk of the material, such as by mixing the com: pound with an inert diluent or carrier, the application to growing plants and soil can be achieved more readily. Such carriers may be either solids, such as talc, clay, diatomaceous earth, sawdust, calcium carbonate or the like, or liquids such as Water, kerosene, acetone, benzene, toluene, xylene, and the like, in which the active Compound may be dissolved or dispersed.

Emulsifying agents preferably are used to achieve a suitable emulsion or dispersion in liquids such as water to give aqueous sprays. Emulsifying agents and wetting agents may also be used to aid in dispersing the active compound in liquids used as the carrier in which the compound is not completely soluble and to increase coverage by the active compound. Emulsifying agents and wetting agents, also known as surface active agents,

are sold under numerous trademarks and may be either pure compounds, mixtures of compounds of the same general group, or they maybe mixtures of compounds of different classes.

There are thus also provided by this invention novel herbicidal compositions containing one or more of the described cycloalkanecarboxamides intimately dispersed with or dissolved in a surface active agent. Typical satisfactory surface active agents which may be used are the alkali metal higher alkylarylsulfon-ates such as sodium dodecylbenzenesulfonate and the sodium salts of alkylnaphthalenesulfonic acids, fatty alcohol sulfates such as the sodium salts of the monoesters of sulfuric acid with n-aliphatic alcohols containing about eight to eighteen carbon atoms, long chain quaternary ammonium compounds, sodium salts of petroleum derived alkylsulfonic acids, polyethylene sorbitan monooleate, alkylarylpolyether alcohols, water-soluble lignin sulfonate salts, alkalicasein compositions, long chain alcohols usually containing about ten to eighteen carbon atoms, and condensation products of ethylene oxide with fatty acids, alkylphenols or mercaptans.

Other additives such as a lanolin or kerosene emulsion, or Tween-20 (a product described -as sorbit-an monolaureate polyoxyalkylene derivative), stickers and other auxiliary materials may be included in solidor liquid formulations to increase coverage of the active compound. These materials are also considered to be surface active agents.

The above descriptions and particularly the examples are set forth for purposes of illustration only. Many variations and modifications thereof will be obvious to those skilled in the art and can be made without departing from the spirit and scope of the invention herein described.

What is claimed is:

1. Cycloalkane carboxamide conforming to the formula:

wherein R is selected from the group consisting of alkyl groups, which contain 1 to 8 carbon atoms and fluorine, chlorine, bromine and iodine, and X and X are independently selected from the group consisting of hydrogen, fluorine, chlorine and a methyl group with the further provision that at least one of said X constituents is selected from the group consisting of chlorine and fluorine.

References Cited by the Examiner UNITED STATES PATENTS 2,337,846 12/1943 Coleman et a1. 260561 2,677,705 5/1954 Utzinger 260557 2,692,282 10/1954 Brown 260557 2,723,192 11/1955 Todd 712.6 2,764,478 9/1956 Searle 712.6 2,784,226 3/ 1957 Brown 260563 2,863,752 12/ 1958 H-amm et a1. 260--562 OTHER REFERENCES Markees et a1.: Jour. Am. Chem. Soc., vol. 71, pp. 203-5 (1949).

Kleene: Jour. Am. Chem. Soc., vol. 63, pp. 3538-9 (1941).

Fischer et aL: (1957).

Cox et al.: Jour. Am. Chem. Soc., vol. 83, pp. 2719- 2724 (1961).

WALTER A. MODANCE, Primary Examiner.

NICHOLAS S. RIZZO, Examiner.

R. PRICE, N. TROUSOF, Assistant Examiners.

German Auslegeschrift 1,005,784 

1. CYCLOALKANE CARBOXAMIDE CONFORMING TO THE FORMULA: 